PROCESS FOR MANUFACTURE OF TRICHLOROTRIFLUOROETHANES

Abstract: A process for producing a reaction product comprising C2C13F3 substantially free of 1,2-dichlorotetrafluoroethane is disclosed. The process includes contacting a feed mixture consisting essentially of compounds of the formula C2Cl4-xF2+x (where x is 0 or 1) wherein the C2Cl4F2 content is between about 10 mole percent and 90 mole percent of said C2Cl4-xF2+x and wherein the mole ratio of the total amount of CCl2FCCl2F and CCl2FCClF2 to the total amount of CCl3CClF2 and CCl3CF3 is at least about 1:9, with an isomerization catalyst to produce isomerization product wherein there is less than about 50,000 parts by weight total CCl2FCCl2F and CCl2FCClF2 per million parts by weight total of CCl3CClF2 and CCl3CF3. The isomerization product is contacted with HF in the vapor phase in the presence of a fluorination catalyst comprising trivalent chromium at an elevated temperature below 400 DEG C selected to provide a fluorination product containing C2Cl2F4, C2Cl3F3 and between about 10 and 90 percent of the C2Cl4F2 from the isomerization product, wherein the ratio of CCl2FCCl2F to CCl3CClF2 and the ratio of CCl2FCClF2 to CCl3CF3 are both greater than the ratios thereof in the isomerization product and wherein the molar ratio of CClF2CClF2 to CCl2FCClF2 is less than about 1:9. C2Cl2F4 and a first portion of the C2Cl3F3 from the fluorination product is recovered; and C2Cl4F2 and a second portion of the C2Cl3F3 from the fluorination product is recycled to the isomerization step along with an additional amount of CCl2FCCl2F which is at least equal to the amount of C2Cl2F4 and C2Cl3F3 recovered from the fluorination product and is sufficient to provide the desired feed mixture ratio of C2Cl4F2 to C2Cl4-xF2+x.

Description: • TITLE PROCESS FOR MANUFACTURE OF TRICHLOROTRIFLUOROETHANES FTELD OF THE INVENTION This invention relates to a process for the manufacture of C 2 CI3F3 reaction product from a mixture of C2CI 4 F2 isomers, and more particularly to the manufacture of C2CI3F3 reaction product which is substantially free of CC1F CC1F 2 . BACKGROUND Tetrachlorodifluoroethanes are readily converted to trichlorotrifluoroethanes (C2CI3F3) by using conventional fluorination. The C2CI3F3 product typically contains greater than 98% of the more symmetrical isomer, CCI 2 FCCIF 2 (CFC-113) . CFC-113 can be readily isomerized to its more unsymmetrical isomer, CCI 3 CF 3 (CFC-113a) using aluminum trihalide catalys . CFC-113a can in turn be converted to 1, 1-dichlorotetrafluoroethane (i.e., CCI 2 FCF3 or CFC-114a) by conventional fluorination. CCI 2 FCF3 is of interest as an intermediate to 1,1, 1,2-tetrafluoroethane (i.e., CF3CH2F or HFC-134a) which can be obtained via catalytic hydrogenolysis of its carbon-chlorine bonds using a supported metal hydrogenation catalyst (see e.g., C. Gervasutti et al., J. Fluorine Chem., 1981/82, 19, pgs. 1-20) . HFC-134a is an environmentally acceptable potential replacement for chlorofluorocarbon (i.e., CFC) refrigerants, blowing agents, aerosol propellants and sterilants that are being viewed with concern in connection with the destruction of stratospheric ozone. It is highly desired that the 1, 1-dichlorotetrafluoroethane employed in the hydrogenolysis route to HFC-134a has as low a content of 1,2-dichlorotetrafluoroethane (i.e., CCIF2CCIF2 or CFC-114) as practicable since the presence of CFC-114 during hydrogenolysis can lead to formation of 1, 1,2,2-tetrafluoroethane (i.e., CHF 2 CHF 2 or HFC-134; see e.g., J. L. Bitner et al., U.S. Dep. Comm. Off. Tech. Serv. Rep. 136732, (1958), p. 25) . HFC-134 mixed in HFC-134a may be objectionable for some applications depending on concentration and, since the two isomers boil only 7°C apart, separation of the isomers in high purity is difficult . There remains a need for processes which facilitate the production of CFC-114a substantially free of its isomer, particularly processes which may employ conventional vapor-phase fluorination techniques. This includes processes for producing trichlorotrifluoro- ethane without producing 1, 2-dichlorotetrafluoroethane. SUMMARY OF THE INVENTION A process is provided in accordance with this invention for producing a reaction product comprising C 2 CI3F3 substantially free of 1, 2-dichlorotetrafluoro- ethane. The process comprises the steps of (i) contacting a feed mixture consisting essentially of compounds of the formula C2Cl _ x F 2 -t (where x is 0 or 1) wherein the C 2 CI 4 F 2 content is between about 10 mole percent and 90 mole percent of said C2CI 4 - X F 2 + and wherein the mole ratio of the total amount of CCI2FCCI2F and CCI2FCCIF2 (i.e., the more symmetric C 2 CI - X F2+ X isomers) to the total amount of CCI3CCIF 2 and CCI3CF3 (i.e., the more unsymmetric C2CI 4 - X F2+ isomers) is at least about 1:9, with an isomerization catalyst to produce isomerization product wherein there is less than about 50,000 parts by weight total CCI 2 FCCI 2 F and CCI2FCCIF2 per million parts by weight total of CCI3CCIF2 and CCI3CF3; (ii) contacting the isomerization product with HF in the vapor phase in the presence of a fluorination catalyst comprising trivalent chromium at an elevated temperature below 400°C selected to provide a fluorination product containing C2CI2F 4 , C2CI3F3 and between about 10 and 90 percent of the C 2 CI 4 F 2 from the isomerization product, wherein the ratio of CCI2FCCI2F to CCI3CCIF 2 and the ratio of CCI2FCCIF2 to CCI3CF3 are both greater than the ratios thereof in the isomerization product and wherein the molar ratio of CCIF2CCIF2 to CCI2FCCIF2 is less than about 1:9; (iii) recovering the C2CI 2 F 4 and a first portion of the C 2 CI3F3 from the fluorination product; and (iv) recycling C2CI 4 F 2 and a second portion of the C 2 CI3F3 from the fluorination product to step (i) along with an additional amount of CCI2FCCI2F which is at least equal to the amount of C2CI2F and C2CI3F3 recovered in step (iii) and is sufficient to provide said feed mixture ratio of C2CI4F2 BRIEF DESCRIPTION OF THE DRAWING FIG. 1 is a schematic representation of an embodiment of this invention. DETAILED DESCRIPTION OF THE INVENTION The process of this invention involves the vapor- phase catalytic fluorination of a mixture of tetra- chlorodifluoroethane isomers. CCI2FCCIF 2 reaction product substantially free of CCIF 2 CCIF 2 is produced. The C2CI 4 F 2 is present in the mixture of halogenated hydrocarbons used in the fluorination step in a molar ratio of CFC-112 to CFC-112a from about 19:1 to 1:19. Preferably, the ratio of CFC-112 to CFC-112a is less than about 1:1, and more preferably is less than about 1:9. In accordance with this invention, the fluorination is under conditions where there is no substantial production of CCIF2CCIF2 (e.g., at an elevated temperature no higher than about 400°C) . No substantial production of CCIF2CCIF2 means herein that the molar ratio of CCIF2CCIF2 to CCI2FCCIF2 in the fluorination product is less than about 1:9. Preferably, the molar ratio of CCIF2CCIF2 to CCI2FCCIF2 in the fluorination product is less than about 1:19, and more preferably is less than about 1:99. The fluorination process according to the present invention can be conducted batchwise, but is preferably conducted continuously in a manner generally known to the art for conducting catalyzed vapor phase fluorination reactions. The C2CI 4 F2 mixtures are reacted with hydrogen fluoride using a catalyst comprising trivalent chromium. In addition to a catalytically effective amount of trivalent chromium, such fluorination catalysts can include other components to increase catalyst activity and/or life such as one or more divalent metal ions (e.g., zinc, mangesium, and/or cobalt) . The trivalent chromium catalyst may be unsupported (e.g., Cr 2 θ3) or supported (e.g., on alumina, aluminum fluoride, magnesium fluoride or carbon) . Suitable vapor-phase fluorination catalysts include trivalent chromium halides (e.g., CrCl 3 and/or CrF3) supported on carbon. A preferred catalyst is CrF3 on carbon and is disclosed in U.S. Pa.t. No. 3,632,834, the contents 'of which are incorporated herein by reference. While any suitable carbon support may be used, a preferred carbon support is acid-washed prior to depositing trivalent chromium on it. Suitable trivalent chromium catalysts may be prepared by treating the carbon used as catalyst support with an acid, preferably with two acids . Typically the support is washed with deionized water after acid treatment and dried; and the chromium halide is then deposited thereon using deposit techniques well known in the art (see e.g.. Example 1 of U.S. 3,632,834) . Preferably, the chromium content (expressed as CrCl3) is from about 5 to 50 weight percent of the carbon-supported catalyst. Acid treatment typically uses an acid other than hydrofluoric acid. Preferred acids used for the acid treatment contain neither'phosphorus nor sulfur. Examples of acids which may be used in the first acid wash during the catalyst preparation process include organic acids such as acetic acid and inorganic acids, such as HC1 or HNO 3 . Preferably hydrochloric acid or nitric acid is used. The second acid treatment, when employed, advantageously uses hydrofluoric acid. Normally, the carbon is treated with acid such that after such treatment the carbon contains less than about 0.1% by weight ash. Commercially available carbons which may be treated with acids to provide suitable supports include those sold under the following trademarks: Darco™, Nuchar™, Columbia SBV™, Columbia MBV™, Columbia MBQ™, Columbia JXC™, Columbia CXC™, Calgon PCB™, Norit™ and Barnaby Cheny NB™. The carbon support can be in the form of powder, granules, extrudates, or pellets, etc. The acid treatment may be accomplished in several ways. A suitable procedure is as follows. A carbon support is soaked overnight with gentle stirring in a 1 molar solution of the acid prepared in deionized water. The carbon support is then separated and washed with deionized water until the pH of the washings is about 3. Preferably, the carbon support is then soaked again with gentle stirring in a 1 molar solution of the acid prepared in deionized water for 12 to 24 hours. The carbon support is then finally washed with deionized water until the washings are substantially free of the anion of the acid (e.g., Cl~ or NO 3 -) , when tested by standard procedures. The carbon support is then separated and dried at about 120°C. The washed carbon is then soaked, if necessary, in 1 molar HF prepared in deionized water for about 48 hours at room temperature with occasional stirring. The carbon support is separated and washed repeatedly with deionized water until the pH of the washings is greater than 4. The carbon support is then dried followed by calcination at about 300°C for about 3 hours in air prior to its use as a support. Reference is made to U.S. Patent No. 5,136,113 for further details relating to producing acid-washed carbon catalysts . For continous processes, the fluorination is generally conducted in the reaction zone for the fluorination. The reaction zone may contain more than one reactor, multiple feed lines, as well as interstage cooling or heating, addition of reactants, diluents, recycle streams, etc. For example, multiple reactors may be used to stage the degree of fluorination so that undue temperature rise and overfluorination are avoided. The reaction product is normally recovered at the end of the reaction zone. If necessary, the reaction products, intermediates and/or by-products can be removed at various stages of the reaction zone and if desired recycled to different parts of the reaction zone. For example, HF and C2CI4F 2 can be fed . to a reaction zone at more than one feed location. CCI 2 FCCIF 2 (CFC-113), is generally recovered from the end of the reaction zone. Suitable fluorination reaction temperatures are normally from about 250°C to 400°C. A preferred temperature range is from 275°C to 375°C, with temperatures ranging from 300°C to 350°C being particularly preferred. The HF to C 2 CI 4 F 2 ratio is normally from 0.2:1 to 4:1, and preferably ranges from 0.25:1 to 2:1. Pressure is not critical. Atmospheric and superatmospheric pressures (e.g., from about 100 kPa to about 7000 kPa) are the most convenient and are therefore preferred. The above reaction variables together with the catalyst loading are balanced one against the other such that in the fluorination products there is a molar ratio of CCIF2CCIF2 to CCI 2 FCCIF 2 in the product mixture which is less than about 1:9. One skilled in the art will recognize that higher temperatures and higher HF:C2Cl4F2 ratios favor a higher degree of fluorination. The amount of overfluorination can thus be reduced by providing a lower HF:C 2 Cl 4 F 2 ratio and/or lower temperature. Catalyst contact time can also be adjusted in a conventional manner to control fluorination. The product mixture from fluorination normally contains a mixture of C2CI3F3 (almost exclusively CCI2FCCIF 2 ) small amounts of CCIF2CF3 (CFC-115) , CCIF2CCIF2, CCI2FCF3 (CFC-114a), unreacted C2CI4F2 isomers and HF and HC1. The fluorination product is separated such that a portion of the C2CI3F3 (and any C 2 CI 2 F 4 ) in the product mixture is separated from C 2 CI 4 F 2 therein. Typically, conventional separation using one or more distillation column (s) is employed. The separation may also include one or more decanter(s) . During separation by distillation, the lower boiling materials (e.g., HF, HC1, CFC-115). are separated from the CFC-112 isomers. It is noted that azeotropes of HF with various halocarbons such as CCI 2 FCCI 2 F, CCI3CCIF 2 , CCI3CF3, and CCI 2 FCF 3 can form during distillation. The CFC-112 isomers from the fluorination product (which are normally enriched in CFC-112 as a result of selective fluorination of CFC-112a) and a portion of the CFC-113 isomer from the fluorination product are fed along with additional CFC-112 to an isomerization zone, where the CFC-112 is substantially converted to CFC-112a. HF should be removed from the C2CI 4 F2 prior to contact with the isomerization catalyst . The C 2 CI3F3 present in the mixture of C2CI3F3 and C2CI 4 F 2 fed to the isomerizer provides a melting point below the melting point of CCI2FCCI2F, thereby facilitating the desired isomerization. Preferably, the C2CI4F2 content is between about 10 mole percent and 75 mole percent of the C 2 CI 4 - F2 +X fed to the isomerization step; and more preferably the C2CI 4 F2 content is between about 10 mole percent and 50 mole percent thereof. The CFC-112 is isomerized to CFC-112a in the presence of recycled C2CI3F3 using an aluminum chloride catalyst as disclosed in Example IV of U.S. Pat. No. 2,598,411. Isomerization of recycled CCI2FCCIF2 may be accomplished in the same isomerization reactor as used for the isomerization of CFC-112 to CFC-112a. However, in accordance with this invention, the molar ratio of C2CI 4 F2 to C2CI3F3 fed to the isomerization zone is at least about 1:9. The molar ratio of (CCI 2 FCCIF 2 + CCI 2 FCCI2F) to (CCI3CF3 + CCI3CCIF2) in the compounds fed to the isomerization generally at least about 1:9. Many aluminum trihalide catalysts can be employed. A preferred catalyst is an anhydrous aluminum trichloride which has been micropulverized (i.e., mechanically comminuted by crushing, ball milling, rod milling, grinding or the like) to provide a surface area of greater than about 0.8 m 2 /g 'and has been activated by treatment under agitation with at least about 10 g CCI 2 FCCIF 2 per gram of aluminum trichloride. Reference is made to copending U.S. Patent Application Serial No. 08/117,379 for further disclosure of micropulverized catalysts. The CFC-112a is recycled in accordance with this invention to the fluorination step. The CFC-113 recovered from the separation zone also may be isomerized to CFC-113a using the aluminum chloride catalyst as disclosed in Example I of U.S. Pat. No. 2,598,411. As above, preferred catalysts include an activated micropulverized anhydrous aluminum trichloride with a surface area of greater than about 0.8 m /g. The CFC-113a from the isomerization zone can readily be reacted with HF in a reaction zone to afford high purity CFC-114a. The latter compound can then be converted by hydrogenolysis to CH 2 FCF3 (HFC-134a) , a non-ozone depleting refrigerant. Employment of the instant invention is further illustrated by reference to FIG. 1 wherein a mixture of C2CI 4 F2 isomers containing substantial CFC-112 and optionally C 2 CI3F3 isomers containing substantial CFC-113 (i.e., the ratio of CFF-113 to CFC-113a is greater than 100:1) is fed through line (211) to an isomerizer (210) . The isomerizer effluent consisting of a mixture of C2CI 4 F2 isomers containing predominantly CFC-112a and optionally C2CI3F3 isomers containing predominantly CFC-113a is fed through line (212) to a fluorination reactor (220) . HF is fed to reactor (220) through line (221) . The fluorination reactor effluent containing unreacted CCI 2 FCCIF2, unreacted C2CI4F2, HF and HC1 and optionally C 2 CI 2 F isomers containing predominantly CCI 2 FCF3 is fed through line (222) to a distillation column (230) . A mixture of C 2 CI3F3 isomers, HF and HC1 and optionally C 2 CI2F 4 isomers is collected at the top of the column and recovered through line (232) . A mixture of C 2 CI 4 F2 isomers enriched in CFC-112 and C 2 CI3F3 enriched in CFC-113, from the bottom of column (230), is fed through line (231) back to the isomerizer (210) along with additional CFC-112 through line (213) . The reactors and their associated feed lines, effluent lines and associated units should be constructed of materials resistant to hydrogen fluoride, hydrogen chloride and chlorine. Typical materials of construction, well-known to the fluorination art, include stainless steels, in particular of the austenitic type, and the well-known high nickel alloys, such as Monel® nickel-copper alloys, Hastelloy® nickel- based alloys and, Inconel® nickel-chromium alloys. Also suitable for reactor fabrication are such polymeric plastics as polytrifluorochloroethylene and polytetrafluoroethylene, generally used as linings. Practice of the invention will become further apparent from the following non-limiting examples. EXAMPLES General Reaction Procedure A 5/8" (1.58 cm) I.D. Inconel® nickel alloy reactor was charged with a catalyst and heated to 300°C in a flow of nitrogen (25 L/min) for about 20 hours. The temperature was reduced to 175°C and a 2:1 molar ratio of nitrogen and HF was started through the reactor (total flow 100 mL/min) . After one hour under these conditions, the molar ratio of nitrogen to HF was adjusted to 1:3 and the temperature increased gradually over a two hour period to 400°C. The reactor was then brought to the desired operating temperature, the nitrogen flow stopped, and the flow of reactants started. General Analytical Procedure The reactor effluent was sampled on-line with a Hewlett Packard HP 5890 gas chromatograph using a 20 foot (6.1 m) long, one-eighth inch (0.32 cm) diameter, column containing Krytox™ perfluorinated polyether on an inert support and a helium flow of 35 mL/min. Gas chromatographic conditions were 70°C for three minutes followed by temperature programming to 180°C at a rate of 6°C/minute. The table percentages are in mole% . EXAMPLE 1 Fluorination of CCI2FCCI2F/CCI2FCCIF2 Mixtures The General Reaction Procedure was followed using a 29% CrCl3 on carbon catalyst (10.8 g, 25 mL) , a molar composition of chlorofluorocarbons (CFCs) containing CC1 FCC1 2 F (64.7%), CCI2FCCIF2 (35.1%), and CCI3CF3 (0.2%), an HF:CFCs molar ratio of 2:1 and a contact time of 30 seconds. The reaction was run at atmospheric pressure. The results at -various temperatures are shown in Table 1. Table 1 Temp. (°C) 115< a > 114(b) 114a< c > 113<d) 113a< e > 112/a< f > 325 0.2 1.6 1.3 55.1 0.2 41.0 350 0.4 4.6 1.9 69.3 0.3 22.7 375 0.9 9.7 3.6 73.7 0.4 10.3 < a >115 is CC1F 2 CF 3 (b) 114 is CCIF2CCIF2 (c) 114a is CCI2FCF3 (d) 113 is CC1 2 FCC1F 2 (e) 113a is CCI3CF3 (f) 112/a is CCI2FCCI2F + CCI3CCIF2 (The isomers of C2CI 4 F2 cannot be distinguished using the above analytical method. In this example it is believed that the product consists essentially of CC1 2 FCC1 2 F) . Other products identified include CF3CF 3 , CC12=CC1F, CCI3CCI 2 F and CCl2=CCl2. EXAMPLE 7 Fluorination of CCI3CCIF2/CCI2FCCIF2 Mixtures The General Reaction Procedure was followed using a 29% CrCl3 on carbon catalyst (10.8 g, 25 mL) , a molar composition of chlorofluorocarbons (CFCs) containing CCI3CCIF2 (63.8%), CCI2FCCIF2 (35.8%), and CCI3CF3 (0.2%), an HF:CFCs molar ratio of 2:1 and a contact time of 30 seconds. The reaction was run at atmospheric pressure. The results at various temeperatures are shown in Table 2. Table 2 Temp. (°C) 115 114 114a 113 113a 112/a< a > 300 0.1 0.9 0.7 90.9 0.5 6.2 325 0.1 3.2 1.6 90.1 0.4 3.9 350 0.3 6.0 2.1 86.9 0.4 3.9 112/a is CCI2FCCI2F + CCI3CCIF2 (The isomers of C 2 CI 4 F 2 cannot be distinguished using the above analytical method. In this example it is believed that the product consisted essentially of CCI3CCIF2) . Other products identified include CCl2=CClF and CCl2=CCl2• Particular embodiments of the invention are illustrated in the Examples . Other embodiments will become apparent to those skilled in the art from a consideration of the specification or practice of the invention disclosed herein. It is understood that modifications and variations may be practiced without departing from the spirit and scope of the novel concepts of this invention. It is further understood that the invention is not confined to the particular formulations and examples herein illustrated, but it embraces such modified forms thereof as come within the scope of the claims which follow.

Claims: £LΔIM£ 1. A process for producing a reaction product comprising C2CI3F3 substantially free of CCIF2CCIF 2 , comprising the steps of: (i) contacting a feed mixture consisting essentially of compounds of the formula C2CI - X F2+ X wherein x is 0 or 1 wherein the C2CI 4 F2 content is between about 10 mole percent and 90 mole percent of said C2CI 4 - X F2+ and wherein the mole ratio of the total amount of CCI2FCCI2F and CCI2FCCIF2 to the total amount of CCI3CCIF2 and CCI3CF3 is at least about 1:9, with an isomerization catalyst to produce isomerization product wherein there is less than about 50,000 parts by weight total CCI2FCCI2F and CCI2FCCIF2 per million parts by weight total of CCI3CCIF2 and CCI3CF3; (ii) contacting the isomerization product with HF in the vapor phase in the presence of a fluorination catalyst comprising trivalent chromium at an elevated temperature below 400°C selected to provide a fluorination product containing C 2 CI2F 4 , C 2 CI3F3 and between about 10 and 90 percent of the C 2 CI 4 F 2 from the isomerization product, wherein the ratio of CCI 2 FCCI 2 F to CCI3CCIF 2 and the ratio of CCI 2 FCCIF2 to CCI3CF 2 are both greater than the ratios thereof in the isomerization product and wherein the molar ratio of CCIF2CCIF2 to CCI2FCCIF2 is less than about 1:9; (iii) recovering the C 2 CI2F 4 and a first portion of the C2CI3F3 from the fluorination product; and (iv) recycling C 2 CI 4 F 2 and a second portion of the C2CI3F3 from the fluorination product to step (i) along with an additional amount of CCI2FCCI2F which is at least equal to the amount of C2CI2F and C2CI3F3 recovered in step (iii) and is sufficient to provide said feed mixture ratio of C2CI 4 F2 to C2Cl 4 _ x F2 + χ. 2. The process of Claim 1 wherein the fluorination catalyst comprises trivalent chromium supported on acid-washed carbon. 3. The process of Claim 2 wherein the fluorination catalyst is a chromium halide supported on acid-washed carbon. 4. The process of Claim 3 wherein the chromium content of the catalyst is from 5 to 50 weight percent expressed as CrCl3. 5. The process of Claim 1 wherein the C2CI 4 F 2 content of the feed mixture is between about 10 mole percent and 75 mole percent of the C2Cl _ x F 2 +χ therein. 6. The process of Claim 1 wherein the C 2 CI 4 F 2 content of the feed mixture is between about 10 mole percent and 50 mole percent of the C2Cl _ x F 2+ therein. 7. The process of Claim 1 wherein the fluorination reaction temperature is from about 250°C to 350°C. 8. The process of Claim 1 wherein the HF:C 2 Cl 4 F 2 ratio for the fluorination step is from 0.2:1 to 4:1. 9. ' The process of Claim 1 wherein the molar ratio of CCIF 2 CCIF2 to CCI2FCCIF2 in the fluorination product is less than about 1:19. 10. The process of Claim 1 wherein the molar ratio of CCIF2CCIF2 to CCI2FCCIF2 in the fluorination product is less than about 1:99.

Inventors: RAO VELLIYUR NOTT MALLIKARJUNA, RAO, VELLIYUR, NOTT, MALLIKARJUNA
Applicants: DU PONT, RAO VELLIYUR NOTT MALLIKARJUNA, E.I. DU PONT DE NEMOURS AND COMPANY, RAO, VELLIYUR, NOTT, MALLIKARJUNA
Application year: 1994
Main classification: C07C19
IPC codes: B01J27, C07B61, C07C17, C07C19